Manufacture of anthraquinone derivatives



Patented Mar. 22, 1932 UNITED STATES PATENT DFFICE W FRANK LODGE AND WILLIAM WYNDHAM TATUM, OF MANCHESTER, ENGLAND, ASSIGNORS TO IMPERIAL CHEMICAL INDUSTRIES LIMITED, OF WESTMINSTER,

ENGLAND MANUFACTURE OF ANTI-IRAQUINONE DERIVATIVES No Drawing. Application filed September 26, 1929, Serial No. 395,461, and in Great Britain October 2, 1928.

This invention relates to the manufacture of anthraquinone derivatives, and consists in a process for the removal of ,B-sulphonic acid groups from l-amino-anthraquinone 2-sulphonic acids by treatment with warm alkaline solution of glucose or other similar polyhydroxylated substance. I

It is known that a-sulphonic groups may be removed from sulphonic acids of the naphthalene and anthraquinone series by reducing agents such as sodium amalgam, or nascent electrolytic hydrogen, but ,B-sulphonic groups resist removal by such methods. v The sulphonic groups, ocor [3-, in homo nuclear substituted anthraquinone sulphonic acids may be removed after reduction to a leuco compound.

We have now made the surprising discovery that afi-sulphonic group in an anthraquinone-fi-sulphonic acid, which contains in the a-position ortho to the ,B-sulphonic group an amino or substituted amino group, is smoothly and completely replaced by hydrogen, without the intermediate production of a leuco-compound, by the action of a warm aqueous alkaline solution of glucose, fructose or other polyhydroxylatedbody which has similar reducing action.

This is remarkable, since alkaline glucose solution is only a mild reducing agent compared with sodium amalgam, sodium hydrosulphite and other agents previously used for the removal of sulphonic groups. The process is all the more extraordinary in that this reagent does not remove sulphonic groups unless they are ortho to an amino or substituted a-amino group; thus l-amino--anilin-o-anthraquinone-2: 8-disulph0nic acid is readily converted by hot alkaline glucose solution into 1-amino4-anilinoanthraquinone-8-sulphonic acid.

Our invention provides a method for the synthesis of various anthraquinone derivatives hitherto diificultly accessible. Thus,

starting from 4-bromo-1-amin0anthraquinone-Q-sulphonic acid ucts are obtained in excellent yield and in very pure condition.

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SOaH

E wampZePrepamti0n 0 f l-amz'no-lt-methylamz'noanthragm'none 10 parts of 1-amino-4c-m-ethylaminoanthraquinone-2-sulphonic acid (such as may be obtained by warming l-amino-t-bromoanthraquinone-Q-sulphonic acid with aqueous methylamine and a copper salt) are heated to 95 C. with 10 parts of glucose and 600 parts of Water, while 20 parts of caustic potash are slowly added. The precipitated violet 1- amino-4-methylaminoanthraquinone is filtered off, washed with hot Water and dried. In place of glucose a corresponding quantity of fructose may be taken.

In an analogous manner the sulphonic acid group may be smoothly eliminated from similar compounds such as l-amino--anilinoanthra'quinone-Q-sulphonic acid, l-aminolp-toluidino anthraquinone-2sulphonic acid, l-ami IlO-tp -amino anilinoanthraquinone-Q- sulphonic acid, 1: 4-diaminoanthraquinone-2- sulphonic acid.

By our invention, alpha-aminoanthraquinones may be prepared from sulphonated aminoanthraquinones having beta-sulphonic groups I in the ortho position to the alpha amino group;]in our process the said sulphonic group is replaced with a hydrogen atom; This replacement of the sulphonic group is efl'ected by means of a mild reducing agent; an aqueous alkaline solution of a polyhydroxylated body having a mild reducing action similar to that of glucose. Glucose and fructose are advantageous. Like compounds having a similar mild reducing action may be used. In our process the reducing agent may be used in at least an amount molecularly equivalent tov the. anthraquinone com-v pound'from which the sulphonic groups are to be removed and replaced by hydrogen.

Our process advantageously converts anthraquinone compounds having the probable r tu X 0 R V SOaH wherein R represents an amino group, R represents a group which is unaffected by aqueous alkaline solutions of glucose, and X represents hydrogen or a sulphonic acid group, into alpha-aminoanthraquinone compounds-having the probable structure ture- E can wherein R represents hydrogen, an alkyl or aryl group, to replace the sulphonic group in the 2-position withhydrogen, thus giving 1'; 4-diaminoanthraquinone compounds which are of commercial value. Many of these compounds are important dyestufis for. acetate silk.

, Among the many compounds which may be prepared by our process the following are typical:

l-aminol anilino-anthraqulnone O NH:

1-amino-4-para-toluidino-anthraquinone OKZQO N NH: it,

There are many specific modifications of our generic invention, the fundamental reactionjof which is the replacement of certain sulphonic acid groups with hydrogen. These sulphonic acid groups are attached to an anthraquinone nucleus in a particular position; first the sulphonic acid group must be ina'beta position and second it must also be ortho to an amino group in the alpha position. By our process, all sulphonic acid groups, so attached to an anthraquinone nucleus are replaced with hydrogen. 7 f VVhat' we claim and desire to Letters Patent is 1-. In the manufacture of alpha-aminoanthraquinone compounds from sulphonated alpha-aminoanthraquinone compounds containing abeta-sulphonic acid group ortho to an amino group in the alpha position, the process which comprises reacting such sulphonated alpha aminoanthraquinone compounds with an aqueousalkaline solution of a polyhydroxylated reducing body of the glucosetype, thereby replacing said beta-sulphonic acid group by hydrogen.

2. In the manufacture of l-amino-anthraquinone compounds from l-aminoanthraquinone-Q-sulphonic acid, the process which comprises reacting 1-aminoanthraquinone-2- sulphonic acid compounds with'an aqueous alkaline solution of glucose, thereby replacing the sulphonic acid group by hydrogen to give a li-aminoanthraquinone compound. 3; In the manufacture of anthraquinone secure by compounds having the probable structural formula wherein R represents an amino group, R represents a group which is unaffected by aqueous alkaline glucose solution, and X represents hydrogen or a sulphonic group, the process which comprises reacting an anthraquinone compound having the probable formula x E R, V (1 son:

wherein R, R and X have the same significance as above, with an aqueous alkaline solution of a polyhydroxylated reducing body of the class consisting of glucose, fructose and compounds having a mild reducing action similar to that of glucose.

4. In the manufacture of anthraquinone compounds having the probable structural formula X [0 NH:

wherein R represents an amino, alkyl-amino or aryl-amino group and X represents hydrogen or a sulphonic group, the process which comprises reacting anthraquinone compounds having the probable formula 0 NHa compounds having the probable structural formula E N-Rs wherein R represents hydrogen, methyl, phenyl, tolyl, or amino-phenyl group, and X represents hydrogen or a sulphonic group, the process which comprises reacting anthraquinone compounds having the probable formula X 0 N H! ii 0 N-Rs wherein R reprensents hydrogen, methyl, phenyl, tolyl or amino-phenyl group and X represents hydrogen or a sulphonic group, with an aqueous alkaline solution of a polyhydroxylated reducing body of the class consisting of glucose, fructose and compounds having a mild reducing action similar to that of glucose.

8. In the manufacture of anthraquinone compounds having the probable structural formula j O N Ha ll (10 g N--R: t

wherein R represents hydrogen, an alkyl or aryl group, the process which comprises reacting anthraquinone compounds having the probable formula dir N-Rs

wherein R represents hydrogen, an alkyl or aryl group with an aqueous alkaline solution 1 of a polyhydroxylated reducing body of the class consisting of glucose, fructose and compounds having a mild reducing action similar to that of glucose.

9. In the manufacture of an anthraquinone 1 compound having the probable structural V formula a v NH: up

the process which comprises reacting an anthraquinonecompound having the probable formula v p (l ii sorn E W.

with an aqueous alkalinesolution of glucose. 10. In the manufacture of anthraquinone compounds having the probable structural formula wherein R represents an alkyl group, the process which comprises reacting anthraquinone compounds having the probable formula O NH:

@ Q-som the process; which comprises reacting an anthraquinoneicompound having the probable formula O NH: 7

(I son:

with an aqueous alkaline solution of a polyhydroxylated reducing body of the class consisting of glucose, fructose and compounds having a mild reducing action similar to that of glucose. I v

12. In themanufacture of anthraquinone compounds having the probable structural formula 0 N H: t (10 (l N-Ra wherein R represents a benzene residue, the

process which comprises reacting anthraqulnone compounds having the probable formula fl N-Ri I I wherein R represents a benzene residue With an aqueous alkaline solution of a polyhydroxylated reducing body of the, class consisting of glucose, fructose and compounds having a mild reducing action similar to that of glucose.

13.; In the manufacture of anthraquinone compounds having the probable structural formula wherein R represents a phenyl, tolyl or phenyl-amino group, the process which comprises reacting anthraquinone compounds having the probable formula y I I I T BOaH I V, i I NR| I whereinR represents a phenyl, tolyl or phenyl-amino group with an, aqueous alkaline solution, of a polyhydroxylated reducing body of the class consisting of glucose, fructose and compounds having a mild reducing action similar to that of glucose.

14. In the manufacture of l-aminoA-aminoanthraquinone 2 sulphonic acid compounds having the probable structural formula wherein R represents an aryl group, the process which comprises reacting a l-amino- -aryl-aminoanthraquinone-2-sulphonic acid with an aqueous alkaline solution of glucose, the said aqueous alkaline solution having a mild reducing action, thereby replacing the sulphonic acid group with hydrogen.

15. In the manufacture of l-aminol-paraanilinoanthraquinone, the process which comprises reacting l-amino-4-para-anilino-anthraquinone-EZ-sulphonic acid, with an aqueous alkaline solution of glucose.

16. In the manufacture of l-aminol-paratoluidino-anthraquinone, the process which comprises reacting l-amino-et-para-toluidinoanthraquinone-2-sulphonic acid with an aqueous alkaline solution of glucose.

17. In the manufacture of l-amino-t-paraamino-anilino-anthraquinone, the process which comprises reacting1-amino-4-para-anilinoanthraquinone-2-sulphonic acid with an aqueous alkaline solution of glucose.

In testimony whereof we afiix our sig natures.

FRANK LODGE. WILLIAM WYNDHAM TATUM. 

